JPS60153943A - Metal component-carbon fiber composite - Google Patents

Abstract

PURPOSE:To enhance the reproducibility or life of a catalyst, by supporting a metal component by a carbon fiber in an uniformly dispersed state. CONSTITUTION:A metal compound being a stock material of a metal component is dissolved in a spinning stock solution of an acrylic fiber and said spinning stock solution is subsequently spun. The fiber having the metal component deposited thereto is heated in an oxidative atmosphere such as air to be converted to an oxidized fiber. This oxidized fiber is heated to a high temp. in an inert atmosphere such as N2, Ar or He and carbonized.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite body in which a metal component is supported on carbon fibers.

Conventionally, as a composite material in which a metal component is supported on carbon fiber, it is known that, for example, carbon fiber is impregnated with a metal component having catalytic ability and then adhered thereto, and the resulting fiber is used as a catalyst. Methods for producing activated carbon fibers are also known, for example, from Japanese Patent Publication No. 54-2297, Japanese Patent Publication No. 55-104910 and Japanese Patent Application Laid-Open No. 56-50107.

However, in the composites produced by such conventional methods, it is difficult to uniformly disperse the active ingredient in the carrier, and the manufacturing conditions for the carrier and the conditions for supporting the active ingredient are strict, so the composites obtained There were problems with the reproducibility and lifespan of the catalyst.

Incidentally, the Fischer-Tropsch synthesis method is known as a method for producing hydrocarbons from a CO+H2 mixed gas, and is currently being operated on an industrial scale in the Republic of South Africa.

Catalysts for producing lower olefins from such mixed gases are typically produced by Ruhrchemy in West Germany.
) iron alloy catalyst, e.g. Fe-V-ZnO-20
etc., and lower olefins such as ethylene and propylene are obtained with high selectivity. However, this catalyst has a problem in reproducibility, and it is difficult to obtain consistent results.

Therefore, the present invention was made in view of the current situation, and since the manufacturing method is simple and it is manufactured as an integrated composite system, the dispersion of metal components can be made uniform.
In addition, it is easy to control the degree of dispersion and particle size of the metal component, and when a metal with catalytic ability is used as the metal component, problems such as reproducibility and life of the catalyst can be fundamentally solved. and ethylene from CO+H2 mixed gas,
It has the advantage of being able to obtain lower olefins such as propylene with high selectivity, and also being able to keep the production rate of methane at a low level.

That is, the metal component-carbon fiber composite of the present invention is characterized in that the metal component is composited and integrated with the carbon fiber, and the metal component is uniformly dispersed throughout the inner and outer layers of the carbon fiber. .

The composite of the present invention has a metal component dispersed on carbon fibers,
It is carried.

As the metal component used in the present invention, for example, conventionally,
All of the catalyst components used for producing hydrocarbons from the above-mentioned mixed gas can be used, and include iron, cobalt, nickel, rhodium, palladium, platinum, titanium, zirconium, vanadium, molybdenum, and the like. The content of the metal component depends on the use of the composite of the present invention, which will be described later, and the manufacturing method thereof. For example, the manufacturing method in which fine particles of a metal compound, which will be a raw material for the metal component, are dispersed in an acrylic fiber spinning dope, which will be described later. If adopted, it can be determined depending on the dispersibility range of the metal compound into the acrylic fiber spinning dope.

Furthermore, if a manufacturing method is adopted in which a metal compound serving as a raw material for the metal component is dissolved in the acrylic fiber spinning dope, the content of the metal component can be appropriately selected within the solubility range of the metal compound.

Alternatively, when using an acrylic fiber containing a compound in which a metal component is bonded in the form of an ionic bond, a complex salt, a complex, etc. as a copolymerization component of an acrylic copolymer as a raw material for carbon fiber, the copolymer The content rate of the metal component can be appropriately selected depending on the content of the component.

The metal component-carbon fiber composite of the present invention is manufactured as follows.

(1) A method using acrylic fibers in which a metal compound is uniformly dispersed, which is obtained by melting a metal compound, which is a raw material for a metal component, in a spinning dope for acrylic fibers, and then spinning the spinning dope.

(2) A method using acrylic fibers in which metal compounds are uniformly dispersed, which is obtained by dispersing a metal compound in a spinning solution for acrylic fibers and then spinning the spinning solution.

(3) A compound in which a metal component is bound in the form of an ionic bond, a complex salt, a complex, etc. is used as a copolymerization component of the acrylic copolymer, and a fiber made of an acrylic copolymer that is copolymerized with this compound is used. Method.

To explain method (1) using an example in which the metal compound is an iron compound, trisacetylacetonatoiron(III)Fe (CII3COCHCO) is added to the spinning dope for acrylic fiber.
CH3)3 is melted to produce a homogeneous solution.

This solution is spun in a coagulation bath according to the methods for spinning acrylic fibers, ie, wet, dry, and dry/wet spinning methods, to produce acrylic fibers in which iron trisacetylacetonate is uniformly dispersed. Trisacetylacetonatoiron (, l [[) is converted into iron hydroxide (iron hydroxide (
III) is deposited in the fiber.

Fe(CH3COCHCOCH3)3 + 3NaOH
→Fe (OH)3 + 3CH3COCHCOCH3
Next, the fibers on which the iron hydroxide (I [ When the iM oxidized fibers are heated to a higher temperature and carbonized in an inert atmosphere such as nitrogen, argon, helium, etc., the metal of the present invention is formed in which the metal component (usually a metal oxide) is composited and integrated with the carbon fiber. A component-carbon fiber composite is obtained.

Furthermore, the metal component-carbon fiber composite may be activated by treating it in water vapor or carbon dioxide according to a known method for producing activated carbon fibers. In this case, the surface area of the composite may be Since the amount increases significantly, the performance as a catalyst can be increased, for example.

The carbonization temperature is not particularly limited, and ordinary carbonization conditions for carbon fibers can be used as they are, for example, 1000°C.

Due to this carbonization, iron (III) hydroxide changes to Fe2O3, and it is thought that this Fe2O3 is dispersed in the carbon fiber as a metal component.

When the metal compound is insoluble in the spinning dope for acrylic fibers, the composite of the present invention can be produced by the method (2) above.

That is, if the metal compound as a raw material is pulverized into fine particles of 0.5μ or less, and this is uniformly dispersed in the spinning stock solution to make it cloudy, it is spun, and then this is carbonized in the same manner as in method (1). An inventive complex can be obtained.

In this case as well, it is thought that the metal compound is changed into a metal oxide and supported on the carbon fibers.

The metal component-carbon fiber composite of the present invention produced in this way is in the form of a fiber in which the metal component is uniformly dispersed and supported on the carbon fibers, and may be used as it is in the form of a fiber. It can also be used in shapes such as cross, felt, and other freely processed shapes.

As described above, the metal component-carbon fiber composite of the present invention can be produced by dissolving or dispersing the raw metal compound in the fiber spinning dope, which is the raw material for the raw material fiber for producing carbon fibers. Since the raw material is acrylonitrile copolymer fibers that are spun or copolymerized with copolymerized components in which metal components are bound in the form of ionic bonds, complex salt complexes, etc., the dispersion of metal components can be easily uniformized. I can do it.

In addition, by controlling the spinning conditions and carbonization conditions of raw material fibers according to conventional acrylic fiber manufacturing conditions and carbon fiber manufacturing conditions, we can control the degree of dispersion of metal components and the particle size of metal components supported on carbon fibers. Can be easily controlled.

According to the present invention, all the metal compounds that can be uniformly dissolved or dispersed in the raw fiber spinning dope for carbon fiber production, without volatilizing or escaping under appropriate carbonization conditions, can finally be dissolved or dispersed. The composite according to the present invention can be made of materials that can be dispersed and remain in the carbon fiber matrix.

Therefore, when the composite of the present invention is used, for example, as a catalyst, it can easily solve the problems of reproducibility and lifespan seen in conventional catalysts.

Furthermore, the composite of the present invention can be manufactured by a simple method as described above, and there are no particularly severe restrictions on manufacturing conditions, making the composite manufacturing economically advantageous.

The uses of the composite of the present invention will be described below.

When the A6 gold metal content is iron-based, it can be suitably used for hydrocarbon production from CO + H2 mixed gas, and 02
It can increase the production of ~C4 olefins and reduce the amount of methane produced, and is suitable as a catalyst for producing 02~C4 olefins.

In addition, if the metal component is a platinum metal, it can be used as a catalyst for hydrogenation of unsaturated bonds in organic compounds or dehydrogenation of saturated hydrocarbons.
As a hydrogenation catalyst for phenol, nitrile, etc., the nickel sulfide-based composite can be used as a catalyst for hydrogenolysis of sulfur compounds, a catalyst for partial hydrogenation of diolefins to monoolefins, and the like.

B9 The composite of the present invention can be used as an electrode material for organic electrode reactions.

For example, it can be used in the following electrode reduction reaction.

A mixed solution is used, and the platinum complex of the present invention is used for the cathode (reduction reaction side electrode).

A p-phenylenediamine derivative can be obtained by partitioning an anode chamber and a cathode chamber with a cornea such as a glass filter, supplying a p-nitrosoaniline derivative to the cathode chamber, and allowing the reaction to occur under appropriate electrolytic conditions.

The obtained p-phenylenediamine derivative can be used as a raw material for a photosensitizer.

C8 can also be used as an electrode for electrolytic oxidation reactions.

For example, a platinum-carbon fiber composite according to the present invention is used.

As mentioned above, as shown in B and C0, the advantage of using a metal component-carbon fiber composite as an electrode material for organic electrode reaction is that the metal component can be supported on the electrode by a method such as impregnation using a normal carbon material as a carrier. Compared to carbon fibers, the metal components are uniformly dispersed in the carbon fibers, so the metal components are strongly fixed to the carbon fibers and are less likely to be dissolved in the electrolyte solution or worn out. Furthermore, by widely controlling the adjustment conditions of the composite itself to obtain an electrode to optimize conditions for electrode reactions such as current efficiency, it is possible to widely control the degree of dispersion of metal components, particle size, etc. control, and the optimum electrode material can be easily found.

D. Application to sensor materials For example, when a surface reaction type gas sensor uses a FeO sintered body as an element, the reducing gas in the detection gas and F
e Utilizing the surface reaction with O, the electrical conductivity or magnetic change (detected by inductance change) of the sintered body is detected, and the target reducing gas (-carbon oxide, methane, propane, etc.) concentration can be determined. Detect.

In addition, the surface adsorption type sensor uses 5n02, ZnO, etc. as an element and detects a change in electrical conductivity due to adsorption of an electron-donating gas.

In the case of these sensors, it is said that there are problems such as changes in performance over time due to selectivity to gas, growth of crystal particles, etc.

Therefore, it is possible that these problems can be improved by using the composite of the present invention instead of the sintered oxide semiconductor used in these known sensors.

E. Application to ion exchange membranes The metal component-carbon fiber composite of the present invention has better compatibility with ion exchange fluids than a matrix consisting only of carbon fibers, and therefore can stably absorb ion exchange fluids. can be retained.

This type of ion exchange membrane is produced by, for example, processing a metal component-carbon fiber composite into a woven fabric or felt having certain voids, and impregnating and retaining a suitable ion exchange liquid into this. , can be produced.

The obtained ion exchange membrane can be applied as a solid ion exchange membrane type ion sensor.

F. Other uses Composites containing and dispersing compounds that serve as magnetic materials or dielectric materials in carbon fibers have magnetic or dielectric properties.
It is expected that new performance will be demonstrated.

Examples of the present invention will be described below.

Example 1 4 g of trisacetylacetonate iron (III) was dissolved in 45 cc of dimethyl sulfoxide (hereinafter abbreviated as DMSO), and this solution was mixed with a spinning stock solution of an acrylonitrile copolymer containing 1.5 mol% of acrylic acid (acrylonitrile). (29g of copolymer/080cc of DNS) and uniformly melted.

This stock solution is processed according to the usual acrylic fiber spinning method.
Mimulation was carried out in an aqueous NaOH coagulation bath. Then, iron trisacetylacetonate (■) decomposed according to the above reaction formula and was deposited in the acrylic fiber as Fe (OH)3. This fiber was processed under normal carbon fiber manufacturing conditions.
Carbonized at ℃ to produce iron component (estimated to be Fe203) -
A carbon fiber composite was obtained. An example of the properties of the obtained metal component-carbon fiber composite is shown below.

Fabric weight: 300 mg/m 5 xi Cross-sectional area: 5.3X10 / Number of single filaments: 3200 Strength: 120 kg/nun2 Modulus of elasticity: 20 tons 7 mm2 Iron content: 3.8% by weight as iron atoms The particle size distribution is shown in the figure.

Example 2 Rho(GO>+e is poorly soluble in DMSO and water, so
This was finely pulverized to 0.5μ or less, dispersed in a spinning dope for acrylic fibers, thoroughly mixed, spun in a coagulation bath, and then carbonized according to the carbon fiber production method using electricity.

As a result, a rhodium component-carbon fiber composite having properties substantially similar to those of Example 1 was obtained.

Example 3 Using the iron component-carbon fiber composite obtained in Example 1, C
O2-C4 olefin production from O+H2 mixed gas was carried out.

First, 1.30 g of the above composite as a catalyst was filled into a heat-resistant glass tube, and 100 ml of hydrogen at 1 atm was heated at 500°C.
Reduction treatment was carried out for 15 hours while the water was running at a rate of 7 minutes. Next, a CO+H2 mixed gas was passed through the prepared catalyst layer under the following conditions while increasing the temperature one after another.

Reaction temperature, reaction gas flow time = 250℃, 6h300℃
, 7h 350℃, 7k+ Reaction pressure: 10Kg/cm2 Mixed gas space velocity: GH3V = 10000 hr
-'The results are shown in the table below.

As is clear from this table, as the reaction temperature was increased sequentially from 250°C to 300°C and 350°C, the conversion rate to ethylene improved.

In addition, no formation of propylene was observed at a reaction temperature of 250°C, but significant formation was observed at 300°C.
At 0°C, the conversion rate was further improved.

Similarly, the conversion rate of butylene also increases as the reaction temperature increases.

On the other hand, although the conversion rate to methane also increases as the reaction temperature rises, the degree of increase with the rise in reaction temperature was low compared to the other olefin components.

[Brief explanation of drawings]

The figure shows the particle size distribution of iron components dispersed in carbon fibers. Sub-agent of the Director of the Agency of Industrial Science and Technology Shin Ogawa, patent attorney of Toshi Co., Ltd. - Patent attorney Ken Noguchi Teru Patent attorney Kazuhiko Saishita 0 4080120160200240280320 Particle size (people)

Claims (1)

[Claims] A metal component-carbon fiber composite in which a metal component is uniformly dispersed and supported on carbon fibers, and the carbon fibers and the metal component are composited and integrated.